Process for effecting water repellency



Unitd htates Patent Oilice 3,284,214 Patented Nov. 8, 1966 3,284,214 PROCESS FUR EFFECTING WATER REPELLENCY Edwin B. Michaels and Clayton A. Wetmore, Norwalk, Conn, assignors to Stamford Chemical Industries, inc, Cincinnati, Ohio, a corporation of Ohio No Drawing. Original application Oct. 4, 1962, Ser. No. 228,247, now Patent No. 3,214,450. Divided and this application Aug. 26, E65, Ser. No. 482,935

9 Claims. (Ci. lilo-2) This application is a division of a copending application for Letters Patent, Serial No. 228,247, filed October 4, 1962, now United States Letters Patent No. 3,214,450.

This invention relates to novel aluminum compounds and to methods for their preparation. More particularly, it relates to organic aluminum compounds containing both ether and ester groups, and has for its object the utilizat-ion of such compounds in compositions that impart Water repellency to fiber, filaments, yarns and fabrics of the natural and synthetic types.

As is known, organic aluminum compounds imparting Water repellency to fabrics have been prepared. For instance, aluminum alcoholates have been reacted with one or two mols of an aliphatic monocarboxylic acid to form condensation products with the elimination of the alcohol. Unfortunately, the utilization of such condensates as water repellent compounds is not a universal practice becauhe the desired resdiual effect on a fabric is not long lasting. The condensates tend to either decompose upon exposure to moistures and/ or behave as gelling agents in most organic solvents.

It has been unexpectedly found that the above difiiculties can be overcome by providing for a particular class of aluminum compounds represented by the general formula:

wherein R is an alkyl or an alkyl substituted phenyl radical, said alkyl containing from 6 to 18 carbon atoms, 11 is an integer from to 6, and R is an aliphatic radical containing from 9 to 17 carbon atoms.

The aluminum hydroxylates of the present invention may be conveniently prepared as follows: An appropriate aluminum alcoholate is reacted with a substantially equimolar quantity of either an alkanol or an alkyl substituted phenol or its ethylene oxide condensation products as prepared by reacting 1 mol of the alkanol or the phenol with from 1 to 6 mols of ethylene oxide. The reaction is continued until 1 mol of an alcohol from the aluminum alcoholate reactant is removed. The latter reaction product is then reacted with one mol of an appropriate aliphatic monocarboxylic acid for a time sufiicient to remove a second mol of the alcohol from the aluminum alcoholate. The order of reaction is not critical and the process can be conveniently carried out even in the presence of all the reactants. Finally, the so-prepared reaction product is then subjected to controlled hydrolysis by providing for the addition of 1 mol of water thereto and removing the third and last mol of alcohol from the aluminum alcoholate originally being treated.

Advantageously, a large variety of aluminum trialcoholates is contemplated herein. Among the preferred alcoholates are: aluminum ethylates, aluminum propylate, aluminum isopropylate, aluminum butylate, aluminum isobutylate, aluminum hexylate and mixturees of the same.

Illustrative alkanols, alkyl substituted phenols, alkanolethylene oxide condensates, and alkyl phenol-ethylene oxide condensates which react with the aluminum alcoholates are: methyl isohutyl carbinol, decanol, t-ridecanol, p-tert-octyl phenol, o-nonyl phenol, p-nonyl phenol, tridecy'lphenol, stearyl phenol and the ethylene oxide condensates thereof prepared by reacting from one to six mols of ethylene oxide per mol of the aforementioned phenol or alkanol.

As the aliphatic monocarboxylic acid reactant, there can be mentioned: decanoic acid, undecanoic acid, lauric acid, d-odecanoic acid, tride-canoic acid, myristic acid, stearic acid, oleic acid and linoleic acid.

Advantageously, each of the aforementioned reactants is commercially available and the overall reaction can conveniently be carried out in the presence of an inert organic solvent. Exemplary solvents are, for instance, naphtha, perchloroethylene, or petroleum ether. The temperature of reaction can widely vary usually between C. and 175 C. A good practice is to employ temperatures between C. and 150 C. for optimum results.

The following examples will serve to more clearly illustrates the invention. These are merely illustrative and are intended not to be construed as being a limitation thereof. Unless otherwise stated, the parts given in this specification are by weight.

Example 1 To a suitable reaction vessel equipped with stirrer, thermometer and condenser are added 204 parts of aluminum isopropylate (1 mol), 206 parts of tert-octyl phenol (1 mol) in 532.5 parts of petroleum ether solvent. The mixture is heated to a temperature of about C. and the temperature is maintained until 60 parts of isopropa- 1101 (1 mol) is collected. Thereafter, 284.5 parts of stearic acid (1 mol) are slowly added with agitation. When 60 parts of isopropanol (1 mol) are additionally removed from the reaction mixture and collected, the reaction product is cooled to about 80 C. Thereafter, 18 parts of water (1 mol) are added thereto and heated to about C. until 60 parts of isopropanol (1 mol) is removed and collected.

On evaporation of the petroleum solvent from the resultant mixture, 532.5 parts of hydroxylated aluminum p-tert-octyl phenoxide stearate is recovered. The latter product is 'solidsoft and waxy to the touch, amorphous and transparent and pale yellow in color. It is soluble in solvents such as benzene, petroleum ether and perchloroethylene.

Example 2 The procedure of Example 1 is repeated in every detail except that aluminum ethylate (1 mol) is employed in place of aluminum isopropylate. During reaction a total of three mols of ethanol is collected and 527.5 of hydroxylated aluminum p-tertaoctyl p'henoxide stearate is obtained.

Example 3 Repeating Example 1 above in every detail except that a condensate of one mol of p-tert-octyl phenol and 1.5 mols of ethylene oxide is employed in plate of the p-tertoctyl phenol reactant of that example. The corresponding p-tert-octyl phenol-ethylene oxide condensate of hydroxylated aluminum stearate is obtained in good yield. The product is a Waxy, soft, amorphous, light brown transparent solid and is soluble in hydrocarbon solvents as toluene and petroleum ether.

Example 4 Repeating Example 1 in every detail except that tridecanol is employed in place of p-tert-octyl phenol. Resultant mixture is then evaporated.

Upon evaporation of the solvent hydroxylated aluminum stearate tridecanoxide is formed in good yield. The product .is a soft, waxy, transparent, amber colored solid soluble in hydrocarbon solvents, such as toluene or petroleum ether.

Example 5 The procedure of Example 1 is repeated in all details except that p-nonyl phenol is substituted for the p-tertoctyl phenol reactant. Resultant products, upon evaporation of the petroleum ether solvent therefrom is hydroxylated aluminum stearate p-nonyl-phenoxide. The latter compound recovered in good yield ,is soluble in organic solvents, such as petroleum ether and benzene. It is a soft, waxy, transparent, light yellow solid.

Example 6 The procedure of Example 1 is repeated in every detail except that methyl isobutyl carbinol is substituted for p-tert-octyl phenol.

The hydroxylated aluminum stearate methyl isobutyl methoxide recovered in good yield upon evaporation of the petroleum solvent is soft, Waxy, transparent solid, soluble in hydrocarbon solvents.

Example 7 Repeating Example 1 in every detail except that oleic acid ,is substituted for stearic acid. Resultant hydroxylated aluminum oleate p-tert-octyl-phenoxide, is recovered in good yield upon evaporation of the petroleum ether solvent. It is a pale amber, soft, waxy, transparent solid, soluble .in benzene or petroleum ether.

Example 8 Substituting lauric acid for oleic acid in Example 7 above, there results hydroxylated aluminum =laurate ptert-octyl phenoxide, soluble in naphtha or perchloroethylene and is a soft, waxy, transparent solid.

Advantageously, the compounds of the invention can be utilized in a water repellent com-position having markedly improved properties. Each of the compounds prepared in Examples 1-8 can be solubilized by dissolving, for instance, 1 to parts of the same .in 1000 parts of perchloroethylene, naphtha or any other equivalent solvent. A suitable wax, such as paraflin or beeswax, in an amount equal to 5 to 25 parts by weight and from 1 to 5 parts by weight of a wax compatible hardening resin such as limed rosin, polymerized terpene resin, or polymerized petroleum resin, are added to the solvent solution. However, the composition may be prepared by any order of addition of the components thereof.

The waterarepellent compositions can be applied to a fabric by any presently known method as, for instance, by dipping, roll coating and the like. Pick up on the fabric from about 1% to about by weight of the hydroxylated aluminum compounds of the invention, based on the weight of the fabric, is usually sufiicient to coat or impregnate the fabric. Upon exposure to a heated atmosphere at temperatures ranging from about 30 F. to about 180 F., the treated fabric is freed from solvent. Advantageously, the fabric remains water repellent after repeated Wear and exposure to normal rainfall. In addition, the fabric can be rendered water-repellent even though it has been previously laundered or drycleaned.

To further illustrate the efiicacy of the compounds of the invention, the following examples are presented.

Exdmplcs 9-18 Three typical fabrics are subjected to treatment to affect their water repellency. Designated as No. 1 is a new unlaundered 6 oz. cotton twill fabric. Designated as No. 2 is a 6 oz. cotton twill fabric which has been drycleaned employing 4% detergent charged naphtha solvent. In the summary tabularized below, these fabrics are treated with a variety of compositions as defined therein.

The method employed in applying the water repellent compositions to fabrics involves the use of seven inch square swatches immersed in an appropriate treating bath. Each swatch is then removed from the solution bath and placed in a basket centrifuge. Extraction occurs and is terminated when the swatch increases to about one-third of its original weight. Extracted fabric is next dried in a circulating air-oven maintained at about 130 F. or higher. The test squares are ironed and tested by subjecting them for sixty seconds to standard spray tests of the American Association of Textile Chemists and Colorists (AATCC).

Referred to in the table herein below is a control solu tion whose composition is as follows:

Component: Parts Perchloroethylene (by vol.) 1000 Parafiin Wax (M.P.=65 C.) 20 Terpene resin (M.P.=115 C.) 12

A variety of commercial available equivalents for each of the above components can be used with equal advantage.

TABLE 2 Spray Ratings on Designated Fabrics Ex. Type of Treatment No. 1 No. 2

9 Fabric untreated O 0 10 Fabric treated with control composition. 70 50 11 Fabric treated with control composition 100 100 containing 1.5% of the Product of of Example 1. 12 Fabric treated with control composition 100 100 containing 2% of the product of Example 2. 13 sflllileils 11 employing product of Exam- 100 p c l4 Fabric treated with control composition 90 containing 2% of the compound prepared by Example 4. 15 Fabric treated with control composition 100 100 containing 2% of the compounds prepared by Example 5. l6 Same as 14 except that 2% of the composi- 100 90 tion prepared by Example 6 is employed. l7 .7 Fabric treated with control composition 100 100 containing 2% of the compound pre pared by Example 7. 18 Fabric treated with control composition 100 90 containing 1% of the composition prepared by Example 8.

In Examples 11 to 8 the AATCC spray ratings are substantially higher than the ratings for the treated fabric of Example 10. The higher the AATCC rating the more effective the treatment.

We claim:

1. A process for rendering matter in the form of a fiber, filament yarn and fabric water repellent by treating the same with an aluminum compound comprising the steps of: applying to said matter a water-repellent composition containing a mixture essentially of (a) from 1 to 10 parts by weight of an aluminum compound in about 1000 parts by volume of a compatible organic solvent, said aluminum compound having the general formula:

rythritol abietate, polymerized terpene resin and polymerized petroleum resin, and thereafter drying the matter so treated, whereby from about 1% to about 15% of said aluminum compound adheres thereto.

2. The process according to claim 1 in which the material treated is a fabric.

3. The process according to claim 1 in which the material treated is a dry-cleaned fabric.

4. The process according to claim 1 in which R, R and n of the aluminum compound are p-octyl phenyl, stearyl and zero, respectively.

5. The process according to claim 1 in which R, R and n of the aluminum compound are p-nonyl phenyl, stearyl and 1.5, respectively.

6. The process according ot claim 1 in which R, R and n of the aluminum compound are p-tertiary octyl phenyl, oleyl and zero, respectively.

7. The process according to claim 1 in which R, R and n of the aluminum compound are methyl isobutyl, isobutyl, stearyl and zero, respectively.

8. The process according to claim 1 in which R, R and n of the aluminum compound are p-nonyl phenyl, stearyl and zero, respectively.

9. A novel composition adapted for rendering matter in the form of a fiber, filament, yarn and fabric waterrepellent comprising a mixture of: (a) from 1 to parts by weight of an aluminum compound in about 1000 where R is a radical selected from the group consisting of alkyl and alkyl-substituted phenyl, said alkyl containing from 6 to 18 carbon atoms, n is an integer from 06, and R is an aliphatic radical containing from 9' to 17 carbon atoms, (b) from 5 to 25 parts by weight of a waxlike substance selected from the group consisting of paraffin and beeswax, and (c) from 1 to 15 parts by weight of a compatible wax hardening resin selected from the group consisting of limed rosin, pentaerythritol abietate, polymerized terpene resin and polymerized petroleum resin. 

1. A PROCESS FOR RENDERING MATTER IN THE FORMULA FIBER, FILAMENT YARN AND FIBRIC WATER REPELLENT BY TREATING THE SAME WITH AN ALUMINUM COMPOUND COMPRISING THE STEPS OF: APPLYING TO SAID MATTER A WATER-REPELLENT COMPOSITION CONTAINING A MIXTURE ESSENTIALLY OF (A) FROM 1 TO 10 PARTS BY WEIGHT OF AN ALUMINUM COMPOUND IN ABOUT 1000 PARTS BY VOLUME OF A COMPATIBLE ORGANIC SOLVENT, SAID ALUMINUM COMPOUND HAVING THE GENERAL FORMULA: R1-COO-AL(-OH)-O-(CH2-CH2-O)N-R WHERE R IS A RADICAL SELECTED FROM THE GROUP CONSISTING OF ALKYL AND ALKYL SUBSTITUTED PHENYL, SAID ALKYL CONTAINING FROM 6 TO 18 CARBON ATOMS, N IS AN INTEGER FROM ZERO TO SIX, AND R1 IS AN ALIPHATIC HYDROCARBON RADICAL CONTAINING FROM 9 TO 17 CARBON ATOMS, (B) FROM 5 TO 25 PARTS BY WEIGHT OF A WAX-LIKE SUBSTANCE SELECTED FROM THE GROUP CONSISTING OF PARAFFIN AND BEESWEX, AND (C) FROM 1 TO 15 PARTS BY WEIGHT OF A COMPATIBLE WAX HARDENING RESIN SELECTED FROM THE GROUP CONSISTING OF LIMED ROSIN, PENTAERYTHRITOL ABIETATE, POLYMERIZED TERPENE RESIN AND POLYMERIZED PETROLEUM RESIN, AND THEREAFTER DRYING THE MATTER SO TREATED, WHEREBY FROM ABOUT 1% TO ABOUT 15% OF SAID ALUMINUM COMPOUND ADHERES THERETO. 